Organic compounds and process of preparing the same



Patented Dec. 22, 1942' Y e ORGANIC COMPOUNDS AND PROCESS or PREPARING THE SAME seam Pitman, N. .L,

de Nemours & Compa corporation. of Delaware Application Octo Serial No. 362,790

I No Drawing.

assignor to-E; L du Pont- Wilmington, Del., a

13 Claims. (01. zoo-404) This invention relates to novel organic compounds and to processesforpreparing the same. More particularly. this invention deals with new methylolamide compounds derived from secv ondaryamidesof higher fatty acids.

Methylol compounds of primary amides, that is compounds of formula RCONH,CH2OH, .are old compounds. Their first preparation was described by Einhorn in Annalen, vol. 343. Compounds of the same series wherein R is a longchain alkyl compound are also described in British Patent No. 463,300 and in U. S. Patents Nos. 2,146,392 and 2,212,654. "These. processes generally involve the treatment of an amide of the formula R-CONHz with formaldehyde in thepresence of an alkaline reagent, such as KzCOa, NaOH or pyridine. Unfortunately, however, the above method has been found inapplicable to secondary amides, that is compounds of'formula R-CONH-Ji', where R is alkyl. Experiments to produce methylol amides of secondary longchain acyl amides by reacting with formaldehyde and an alkaline reagent, gave negative results.

,It is accordingly an object of-this invention to provide a process for preparing N-methylol derivatives of secondary acyl amides. It is a further object of this invention to produce asnovel compounds N-methylol derivatives of secondary long-chain acyl amides, and to test their adaptability for use in imparting water-repellency to textile fiber. Further important objects of this invention, will appear as the description proceeds.

These objects of my invention are accomplished generally by reacting the N methylene halide of a secondary amide with a slightly moist inorganic alkaline reagent in an organic solvent. More particularly, I react-with an alkaline reagent and water upon a secondary amide of the general formula wherein-R is an aliphatic radical free from watersolubilizing groups and being attachedto the CO group above shown either directly or through the agency of an O, S or N atom; R is an alkyl radical, or an alkylene radical carrying an additional group of the form R-CO-NH, as above defined, while X is halogen, for instance chlorine or bromine.

The requisite methylene halide compounds which form the initial material for my process may themselves be prepared by reacting the corresponding'secondary acylamide with formaldehyde and dry hydrogen halide, according to the procedure, for instance, descrlbed in U. 8. Patent No. 2,131,362 or in British Patents Nos. 492,699, 494,761, and 501,480. l

The reaction of the chloromethyl amide and the inorganic base is best carried out in the same solvent in which the reaction of the amide and formaldehyde has been carried out: that is. in benzene, toluene, carbon tetrachloride, cyclohexane, aliphatic hydrocarbons, andother similar solvents. Asinorganlc bases, which may be used for my invention the following may be mentione'd asconvenient: Sodium carbonate, potassium carbonate, sodiumor potassium-hydroxide, magnesium oxide, lime, calcium carbonate, sodium bicarbonate,.or anyother. inorganic base which will not form aquaternary compound. 01 course, sufilcient water should be present in the alkali or should be added tothe reaction mass to provide for the requisite exchange of OH for C1, according to the following typical equation: v RecOIIT-CHQCI+36Kz0Owl-Hi0:RC0NCHz0H+KCl+MCOg The reaction is carried out by agitating the solution of the halogenmethyl compound with a considerable excess, usually, of the basic; material at room temperature. Some heat of reaction is usually evolved and some cooling is necessary.

When the solvent layer becomes free of halogen, the reaction is complete. The product is recovered by filtering out the inorganic salts and evaporating off the solvent.

If R in the above formula contains a long chain, sayan alkyl radical, saturated or unsaturated, of 7 to 29 carbon atoms, the product is a low melting wax and is quite soluble in organic solvents like benzene and carbon tetrachloride. This is a marked difference over the insolubility of the methylol compounds derived from primary amides, and therefore makes the novel compounds much more useful as agents for imparting softness or water-repellency to textile fiber from organic solution.

The novel organic compounds of thi invention react readily with phosphorus trihalides, to produce compounds which after a series of rearrangements give phosphonic acids of the general formula n-coN-cn,-Po om.

in the same manner as the primary methylol amides behave according to copending application of Engelmann 8: Pikl, Serial No. 322,766. Thus, in the case of the compound derived from methyl-stearamide, the series of transformations may be indicated by the following equations:

the novel compounds, and the resulting phosphonic acids may be employed as softening and water-repellency agents for textile flber applica-- ble for aqueous bath. I

Without limiting my invention to any particular procedure, the following examples are given to illustrate my preferred modefof operation. Parts mentioned are by weight.

- Exemplar 1 70 parts of chloromethyl-methyl stearami'de (O lIrCO-Jf-Cflgbl) Example 3 the aqueous layer was separated and the carbon tetrachloride solution cooled at 20 C. and treated with 450 parts of commercial potassium carbonate (containing moisture). Some cooling is necessary at the beginning to keep the temperature around C. After standing for 24 hours the carbon tetrachloride solution was "neutral towards Congo red paper and was filtered. The filtrate presumably contained N,N'- methylene-bis (stearamido-methanol) A solution of this product in G014 was prewere dissolved in 200 parts of benzene, and then 40 parts of commercial potassium carbonate (containing 15% moisture) were added, and the mixture was agitated for 10 hours at room temperature. The potassium chloride-and excess carbonate were filtered off, and the benzene filtrate was evaporated invacuo. The product was a waxy solid, which was shown by the phosphonic acid test to be a methylol compound-of the probable formula -1 C11Hu C'O+-N-CH:OH

. I on. v which may be named jN-meth'yi-stearamidomethanol.

Cotton cloth was impregnated with "a 2% solution of this product in carbon tetrachloride and then heated to 120 to 150 C. for a few minutes. The material acquired strong water-repellent properties and lost only little of it on washing with soap.

If'the cloth was pretreated with a small amount of an acid like oxalic, citric, glycollic, or acetic acid the water-repellency' was decidedly improved.

xamp 2 To 100 parts of the reaction product of octadecyl carbamate, formaldehyde and hydrogen chloride .which was dissolved in 200 parts of carbon tetrachloride, there were added 50 parts of calcium hydroxide. (which has been. exposed to most air), and the mass was agitated at room temperature for 6 hours; After thistime the carbon tetrachloride solution .was, filtered and evaporated. The waxy masswhich remained was free of halogen. Whenapplied from a benzene solution to cloth and then subjected to a-heat treatment at 120 to .150 C. the cloth became strongly water-repellent. I

The. product obtained above was probably mostly the N,N'-me thylene-bis-(octadecyl-carbamido-methanol) of the following formula:

. n y CnHn-O-C-N-CHaOH /CH1 Calla-O-fi-N-CHzOH 0 pared which contained 1% active ingredient, and then small amounts of various auxiliary agents were added to different samples of this solution. Pieces were impregnated with these solutions and then subjected to a heat treatment at 120 to 150C. The best water-repellency was obtained when the solution contained as auxiliary agent a small amount of PCI: (1 drop per pound of solution) thionyl chloride, stearamidomethyl phosphonic acid, stearamido-methyl pyridinium chloride, chloromethyl stearamide, or even mineral acid. The amount of these agents was varied from mere traces inthe case of PC11 up to about 20% of the active ingredient in the case of the phosphonic acid, but it was always kept down to such a concentration that no tendering of the fabric was caused.

Example 4 of dry air and the solution was then reacted at room temperature with 50 parts of sodium bicarbonate. After 10 hours, the solution was neutral to Congo red paper and the inorganic salts were filtered off.

The resulting product had similar properties to the product described in Example 3. Presumably, the action of hydrogen chloride and paraformaldehyde upon stearamide produces essentially methylene bis-(stearamido-methylene chloride), which was then converted into the corresponding bis-methylol compound.

In. the above experiment the sodium bicarbonatemay be replaced with slightly moist magnesium' oxide, moist barium carbonate or calcium. carbonate with the same results.

'Instead of s tearamide, palmitic acid amide, montanic acid amide, and amides from coconut oil acid as well as acids from the paramn oxidation may be used with similar results. Similar results may also be obtained by using octadecyl urea .(CmHavNiL-CONHa) or stearoyl urea (C1vHae-CONH-CONI-Iz) instead of the stearamide above.

.I claim:- 1, The compoundsof the general formula n-co-N-cmon roup through the agency of an atom selected from the group consisting of carbon, oxygen. sulfur and nitrogen, while B. isa radical of the groupconsisting of the alkyl radicals and alkylene radicals carrying a further group of the form R COIIICH:OE

as above defined.

2. A water-repellency agent being a compound as defined in claim 1, wherein R carries an alkyl chain of at least 7 carbon atoms.

3. A compound of the general formula m-qo-n-omon wherein Alk stands for an alkyl radical having from 7 to 29 carbon atoms, while R designates an alkyl radical.

4. A compound of the general formula m-co-m-cmoa AlkC-I ICHa0H wherein Alk stands for an alkyl radical having from 7 to 29 carbon atoms, while R. designates an alkylene radical.

5. A compoundof the general formula Alk-O-C O-N-CHaOH wherein Alk stands for an alkyl radical having from 7 to 29 carbon atoms. while R designates an alkylene radical.

6. N-methyl-stearamido-methanol.

'7. N ,N '-methylene bis- (stearamido-methanol) 8. N,N'-methylene-bis(octadecyl -carba.mido methanol).

9. A'process of preparing an N-methylol derivative ofa secondary organic amide, which comprises reacting with an inorganic, alkaline reagent 7 in the presence-of moisture upon-a" secondary organic amidoe-methylene .h'alide compound of the general formula R--c o-N-cmx water-solubilizing-groups X is a halogen-atom,

while R stands for a radical of the group 'consisting of the methyl radicals and methylene radicals carrying a further group of the form R-CO-If-CHzX wherein R isan aliphatic radical free Krom moisture upon ll-methyl-stearamidc methylene chloride.

12. The process which comprises reacting with an inorganic alkaline agent in the presence of moisture upon N,N'-methylene-bis(stearamidomethylene chloride).

13. The process which comprises reacting with an inorganic alkaline agent in the presence of moisture upon N,N'-methylene-bis (octade'com-lcarbamido-methylene chloride).

JOSE! PIKL.

CERTIFICATE OF CORRECTION. ratent No. 2,306,185. December. 22, 19!;2.

- JOSEF PIE.

It is hereby certifieu that error appears in the printed specification of the above numbered patent requiring correction as follows: Page -2, secand column, line 21, after "Pieces" insert --oi cotton--.; and that the said Letters Patent should be read with this'com ection therem that the aims may cenform to the record of the case in the Patent Office.

Signed and sealed this 16th day of-February, A. D. 1911.}.

Henry Van Arsdell-e, (seal) Acting Commissioner of Patents. 

